Novel nanoporous nitrogen-enriched carbon materials were prepared through a simple carbonization procedure of well-defined block copolymer precursors containing the source of carbon, i.e., polyacrylonitrile (PAN), and a sacrificial block, i.e., poly(n-butyl acrylate) (PBA). The preparation of nitrogen-enriched nanocarbons with hierarchical pore structure was enabled by the high fidelity preservation of the initial phase-separated nanostructure between two polymer blocks upon carbonization. Supercapacitors fabricated from the prepared carbons exhibited unusually high capacitance per unit surface area (>30 μF/cm(2)) which was attributed to the pseudocapacitance resulting from the high nitrogen content originating from the PAN precursor. Electrochemical availability of the nitrogen species was also evident from the results of oxygen reduction experiments. The hierarchical pore structure and the high nitrogen content in such materials make them particularly promising for use in supercapacitor and electrocatalyst applications.

The design of carbon materials for improved electrochemical systems should combine the preferential occurrence of pyridinic functionalities and a structure that maximizes their exposure to the surface. The carbonization of nitrogen‐rich polyacrylonitrile (PAN) retains a high level of nitrogen content, with a large percentage of the functionalities taking the form of pyridinic species at the graphene edges. A block copolymer precursor containing PAN and a second thermally sacrificial block can be converted to a nitrogen‐rich carbon material with a mesoporous network mimicking that of the precursor. Here, we highlight the structural advantages of this templating approach and their improvement in several electrochemical systems.

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